3-alkylsulfonamido-pyridinium salts



Patented June 14, 1949 UNITED STATES PATENT OFFICE S-ALKYLSULFONAMIDO-PYRIDINIUM SALTS Mitchell F. Zienty, Elkhart, Ind., assignor to The Upjohn Company, Kalamazoo, Mich., a corporation of Michigan No Drawing. Application January 28, 1948, Serial No. 4,944

Wherein R represents an alkyl radical having from 8 to 16 carbon atoms, inclusive, R represents hydrogen or an alkyl radical having from 8 to 16 carbon atoms, inclusive, R" represents a lower alkyl, lower alkenyl or aralkyl radical, and Z represents a halogen or an alkylsulfate radical (alkyl-SOr-L They may be designated conveniently as 3N'-alkylsulfonamido pyridinium salts. It is understood that in the present application the symbol N refers to the nitrogen atom of the amido radical.

The quaternary ammonium salts of the present invention are of value as wetting agents, surface tension depressants, detergents and, in particular, as germicides.

They can be prepared readily by warming a mixture of an N-alkyl-3-pyridine sulfonamide and a hydrocarbon ester of an inorganic acid such as 30 an alkyl halide, an alkenyl halide, an aralkyl halide or an alkyl sulfate to a reaction temperature.

The N-alkyl-3-pyridine sulfonamide reactants used in preparing the quaternary compounds of the invention have the generic formula SO:N

wherein R and R have the values given previously. These compounds include, among others, the following: N'-dodecyl-3-pyridine sulfonamide, N'-tetradecyl-3-pyridine sulfonamide, N- hexadecyl-B-pyricline sulfonamide, N',N'-di-(2- ethyl-n-hexyl) -3'-pyridine sulfonamide, N-decyl- 3-pyridine sulfonamide, N'-tridecyl-3-pyridine sulfonamide, N'-(2-ethyl-n-hexyl) 3 pyridine 6 Claims. (01. 260-295) tetradecyl-3-pyridine sulfonamide, N-dodecyl- N'-hexadecyl-3-pyridine sulfonamide, N'-decyl- N'-tridecyl-3-pyridine sulfonamide and N '-undecyl-N-(2-ethyl-n-hexy) -3-pyridine sulfonamide. The nature of the radicals R and R in the quaternary compounds are determined by the N'-alkyl-3-pyridine sulfonamide used in any particular instance. Certain of the N'-alkyl-3- pyridine sulfonamides herein referred to are described and claimed in a con-currently filed, copending application Serial No. 4,943.

Lower alkyl and lower alkenyl radicals referred to herein, and represented by R" in the first general formula given, are those containing less than 7 carbon atoms and include the methyl, ethyl,

propyl, butyl, hexyl, ethenyl, propenyl, allyl, butenyl and pentenyl radicals. Aralkyl radicals represented by R" in the general formula are those containing less than 12 carbon atoms and include the benzyl, phenylethyl, phenylpropyl,

aralkyl radicals are the allyl and benzyl radicals,

sulfonamide, N'-undecyl-3-pyridine sulfonamide, N ',N'-di-dodecyl 3 pyridine sulfonamide, N',N'-di-decyl-3-pyridine sulfonamide, N,N'-diundecyl-3-pyridine sulfonamide, N',N'-di-hexadecyl-3-pyridine sulfonamide, N'-hexadecyl-N- undecyl-3-pyridine sulfonamide, N'-dodecy1-N'- respectively. Non-cyclic radicals referred to herein, and represented by R, R or R", can be either straight or branched chain. Hydrocarbon esters of inorganic acids which can be used in forming the quaternary ammonium compounds include methyl iodide, ethyl chloride, n-butyl bromide, isobutyl bromide, hexyl iodide, allyl bromide, propenyl bromide, butenyl chloride, dimethyl sulfate, diethyl sulfate, benzyl chloride, p-tolylethyl chloride, and many others.

The reaction can be carried out in the presence of an inert liquid diluent, such as an alcohol or a hydrocarbon, or without the use of a diluent, as desired, and at any suitable temperature below the decomposition temperature of the reactants or product. Good yields of product have been obtained by heating the mixture to between about 50 and about C. One of the reactants, or a solution thereof in an inert diluent, can be added portionwise and with mixing to the other reactant at the reaction temperature, if desired, although this is not necessary.

Any suitable proportions of reactants can be employed, any excess of either of the reactants :being removed from the quaternary ammonium compound during the isolation and purification steps. In practice, it has been found desirable to use either equimolecular proportions of the reactants or to employ a substantial excess of the hydrocarbon inorganic ester. "Such excess appears to serve as a solvent for the reactants which favors the reaction and does not materially complicate isolation of the quaternary ammonium compound. Usually not more than 1.5 molecular proportion of hydrocarbon inorganic ester is employed. The reaction is usually substantially complete .in'from a fewminutes to several hours. The reacted mixturecis cooled to about room temperature, or below, to crystallize the quaternary ammonium salt, which is obtained as a white, yellow or tan solid. When a diluent is used in which the reaction product is soluble, isolation is best accomplished by removal of the diluent, preferably under reduced pressure. The crude product thus obtained can be employed without further modification as a constituent of germicidal, wetting or surface tension depressant-com positions or it can be purified further, e. g. by crystallization. Such crystallization is conveniently accomplished by dissolving the crude salt in .a small amount of .a :hot inert solvent, such as ethyl acetate or an acetone-hexane mixture or 9, mixture of petroleum ether and ethyl ether, cooling the solution, separating the precipitated crys: tals by decantation or filtration and drying the crystals thus obtained. The following examples serve to illustrate the invention but are not to be construed as limiting.

EXAMPLE 1 a mixture of benzene and petroleum ether (B. P.

90-100 0.). Eifteen grams of N'-hexadecyl- 3-pyridine sulfonamide was obtained melting at 78-.-'7.9'C.

Other N'-alkyl-3-.pyridine .sulfonamides were prepared in asimilar manner.

EXAMPLE 2 A solution of 1.25 grams of N'-hexadecyl-,3z

pyridine sulfonamide and 0.6 gram of methyl iodide in 15 milliliters of absolute ethanol was refluxed for six hours. The alcohol was evaporated and the yellow residue dissolved in warm ethyl acetate. Upon cooling the solution a precipitate formed which was recovered by filtering and drying. There was-thus obtained 1.5 grams of 3-N'-hexadecylsu1fonamido-1-methy1 pyridinium iodide melting at 165-166 C.

EXAMPLE 3 A mixture of 1. 5 grams of N-hexadecyl-3- pyridinesulfonamide and 0.49 gram of benzyl chloride was heated at C. for two hours. The ,crystalline'.-mass which formed when the mass cooled was crystallized from ethyl acetate. There was thus obtained 1.8 grams of 3-N-hexadecylsulfonamido-l -benzyl pyridinium chloride melting at 161 C.

EXAMPLE 4 A mixture of two grams of N' hexadecyl-gpyridine sulfonamide and 0.75 gram oi dimethyl sulfate was heated at 1Q0 C. for three hours. The unreacted dimthyl sulfate wasyremlov'ed by Washing with petroleum ether. The "semi-solid 3-N-hexadecylsulfonamido-1-methyl pyridinium methosulfate obtained purified by recrystallization from ethyl acetate. The colorless plates obtained weighed 2.1 grams and melted at 104105 C,

EXAMBLE5 A number of aeesN -zalkylsulfonamido pyri dinium salts were prepared substantially a'shy the procedures :given in Examples 2,8 and 4. The melting points of the compounds were deter; mined and they were each analyzed quantitatively for halogen or nitrogen. 'The'germicida'kl effectivenes of each :of the compounds was deter mined by the method of Rue'hle and "Brewer (U. S. D. A. Circular; 198 .4 (1931) A The data obtained is given in the acompanying table and the results expressed in terms of 'thegreatest dilution of the pure individual compound which will kill Staphylococcus aureus in IO'minuteshflt not in 5 minutes at 375 0. Data on the com pounds prepared in Examples 2, 3 and 4 are cluded in the table.

Table 3-N-alkysul fona mido pyridiniumsalts having the generic formula:

Halogen, percent Highest R a a" z '35" Formula Germicidal Calcd Found Dilution 27.03 1-15, 000 v 26.91 1 20,6110 1 24.41 14050110 I l .24..02' 145.1100 GflHwOz'NzSCll 7. 74 7.71 1-30, 000 GzaHuOiNzSGL 7.36 7.16 1-10,.u00 Cg3H45 OzNzSCL 6.39 6.85 1-25.-DDD 111--..-. use 5.82 1-20,000 3 5 7. .7 ,1

CH 1 s0 17 6 1 1mm 16.84 .16. 05 1 1011100 1 5. 00 7 1 5. 70 145.1000 15.110 115.88 0 25:0011

6.19 6. 21 0 '6. 25 -6. 14 H 6:51 5:77 O H -pa 5 51 5. 721? hiEthlil-n hexyl. -Nitmgempercent.

5 I claim: 1. A compound having the general formula R SOzN Z RI! wherein R is a member of the group consistin of the alkyl radicals containing from 8 to 16 carbons, inclusive, R. is a member of the group consisting of hydrogen and the alkyl radicals containing from 8 to 16 carbon atoms, inclusive, R" is a member of the group consisting of the lower alkyl, lower alkenyl and aralkyl radicals, and Z is a member of the group consisting of the alkylsulfate and halogen radicals.

2. A compound as claimed in claim 1 wherein R represents hydrogen.

3. 3-N',N-di-(2 ethyl-n-hexyl) -sulfonamiclol-methyl-pyridinium iodide.

4. 3-N' dodec-ylsulfonamido-l-benzyl-pyridinium chloride.

5. 3-N'-hexadecylsulfonamido-l-allyl-pyridinium bromide.

6. The method which includes: heating a compound having the formula S OgNRR N Z RI! wherein R" represents a member of the group consisting of the lower alkyl, lower alkenyl and aralkyl radicals and Z represents a member of the group consisting of the alkylsulfate and halogen radicals, R and R having the values given. MITCHELL F. ZIENTY.

No references cited. 

